JP7452527B2 - Cold storage material composition - Google Patents

Description

The present invention relates to a cold storage material composition.

Cold storage material compositions are used in fields such as food preservation and medicine to obtain a cold preservation effect. For example, in order to maintain the temperature inside the refrigerator at a low temperature in the event of a power outage, a cold storage material composition is installed inside the refrigerator.

Patent Document 1 discloses a cold storage material composition that is maintained in an unintended temperature range lower than the control temperature for a short time before reaching the control temperature during use after cooling. . This cold storage material composition contains water, a quaternary ammonium salt, and a hydroxyl group-containing organic compound, the quaternary ammonium salt forms a clathrate hydrate, and the hydroxyl group-containing organic compound contains carbon. number is 1 to 12, and the number of hydroxyl groups in one molecule is 0.3 to 1.0 times the number of carbon atoms, and the concentration of the quaternary ammonium salt is less than the saturation concentration, and is 15% by mass or more. The content of the hydroxyl group-containing organic compound is 2.5 to 16% by mass.

Patent Document 1 states in paragraph number 0036 that a more preferable example of a combination of a quaternary ammonium salt and a hydroxyl group-containing organic compound contained in a cold preservation composition is a combination of the following substances (a) and (b). is disclosed.
(a) Either or both of tetra-n-butylammonium bromide and tetra-n-butylammonium fluoride, and (b) methanol, ethanol, 1-propanol, 2-propanol, ethylene glycol, propylene glycol, diethylene glycol , glycerin, sorbitol, mannitol, xylitol, erythritol, glucose, fructose, mannose, arabinose, sucrose, lactose, maltose, trehalose, ascorbic acid, and sodium ascorbate.

Patent Document 2 (particularly paragraph number 0023) and Patent Document 3 (particularly paragraph number 0040) disclose that alcohols are used to lower the melting point of tetra-n-butylammonium bromide.

Patent Document 4 discloses a heat storage material in which potassium alum is added to an aqueous solution containing a tetraalkylammonium salt. Patent Document 5 discloses a heat storage material containing tetra-n-butylammonium bromide hydrate, tri-n-butyl-n-pentylammonium bromide hydrate, and tetra-n-butylammonium fluoride. ing.

Japanese Patent Application Publication No. 2017-179299 Japanese Patent Application Publication No. 2007-163045 Japanese Patent Application Publication No. 2010-018879 Patent No. 6226488 Patent No. 4839903

Mohamed Rady et. al. "A Comparative Study of Phase Changing Characteristics of Granular Phase Change Materials Using DSC and T-History Methods", Tech Science Press FDMP, vol.6, no.2, pp.137-152, 2010

An object of the present invention is to provide a heat storage material composition suitable for refrigerators or cold storages.

The cold storage material composition according to the first aspect of the present invention includes:
Tetra-n-butylammonium bromide,
Contains water and 1-propanol,
The weight ratio of the tetra-n-butylammonium bromide to the water is 37.5/62.5 or more and 40/60 or less,
The molar ratio of the 1-propanol to the water is 0.043 or more and 0.065 or less,
The cold storage material composition has a heat of fusion of 135 joules/gram or more within a range of 2 degrees Celsius or more and 8 degrees Celsius or less, and the cold storage material composition has a heat flow within a range of 2 degrees Celsius or more and 8 degrees Celsius or less. Has a peak.

The cold storage material composition according to the second aspect of the present invention is
Tetra-n-butylammonium bromide,
Contains water and 1-propanol,
The weight ratio of the tetra-n-butylammonium bromide to the water is 32.5/67.5 or more and 42.5/57.5 or less,
The molar ratio of the 1-propanol to the water is 0.02 or more and 0.042 or less,
The cold storage material composition has a heat of fusion of 135 joules/gram or more within a range of 5 degrees Celsius or more and 12 degrees Celsius or less, and the cold storage material composition has a heat flow within a range of 5 degrees Celsius or more and 12 degrees Celsius or less. Has a peak.

The cold storage material composition according to the third aspect of the present invention includes:
Tetra-n-butylammonium bromide,
Contains water and 1-butanol,
The weight ratio of the tetra-n-butylammonium bromide to the water is 30/70 or more and 42.5/57.5 or less,
The molar ratio of the 1-butanol to the water is 0.02 or more and 0.035 or less,
The cold storage material composition has a heat of fusion of 135 joules/gram or more within a range of 5 degrees Celsius or more and 12 degrees Celsius or less, and the cold storage material composition has a heat flow within a range of 5 degrees Celsius or more and 12 degrees Celsius or less. Has a peak.

An object of the present invention is to provide a heat storage material composition suitable for refrigerators or cold storages.

FIG. 1 is a graph showing the results of differential scanning calorimetry of Example A1 and Comparative Example A1. FIG. 2 is a graph showing the results of differential scanning calorimetry of Example A2 and Comparative Example A1. FIG. 3 is a graph showing the results of differential scanning calorimetry of Example A3 and Comparative Example A1. FIG. 4 is a graph showing the results of differential scanning calorimetry of Example A4 and Comparative Example A1. FIG. 5 is a graph showing the results of differential scanning calorimetry of Example A5 and Comparative Example A1. FIG. 6 is a graph showing the results of differential scanning calorimetry of Example A6 and Comparative Example A1. FIG. 7 is a graph showing the results of differential scanning calorimetry of Example A7 and Comparative Example A1. FIG. 8 is a graph showing the results of differential scanning calorimetry of Comparative Example A3 and Comparative Example A1. FIG. 9 is a graph showing the results of differential scanning calorimetry of Comparative Example A7 and Comparative Example A1. FIG. 10 is a graph showing the results of differential scanning calorimetry of Comparative Example A9 and Comparative Example A1. FIG. 11 is a graph showing the results of differential scanning calorimetry of Comparative Example A10 and Comparative Example A1. FIG. 12 is a graph showing the results of differential scanning calorimetry of Comparative Example A18 and Comparative Example A1. FIG. 13 is a graph showing the results of differential scanning calorimetry of Comparative Example A21 and Comparative Example A1. FIG. 14 is a graph showing the results of differential scanning calorimetry of Comparative Example A22 and Comparative Example A1. FIG. 15 is a graph showing the results of differential scanning calorimetry of Comparative Example A26 and Comparative Example A1. FIG. 16 is a graph showing the results of differential scanning calorimetry of Example B1 and Comparative Example B1. FIG. 17 is a graph showing the results of differential scanning calorimetry of Example B2 and Comparative Example B1. FIG. 18 is a graph showing the results of differential scanning calorimetry of Example B3 and Comparative Example B1. FIG. 19 is a graph showing the results of differential scanning calorimetry of Example B4 and Comparative Example B1. FIG. 20 is a graph showing the results of differential scanning calorimetry of Example B5 and Comparative Example B1. FIG. 21 is a graph showing the results of differential scanning calorimetry of Example B6 and Comparative Example B1. FIG. 22 is a graph showing the results of differential scanning calorimetry of Example B7 and Comparative Example B1. FIG. 23 is a graph showing the results of differential scanning calorimetry of Example B8 and Comparative Example B1. FIG. 24 is a graph showing the results of differential scanning calorimetry of Example B9 and Comparative Example B1. FIG. 25 is a graph showing the results of differential scanning calorimetry of Example B10 and Comparative Example B1. FIG. 26 is a graph showing the results of differential scanning calorimetry of Example B11 and Comparative Example B1. FIG. 27 is a graph showing the results of differential scanning calorimetry of Example B12 and Comparative Example B1. FIG. 28 is a graph showing the results of differential scanning calorimetry of Example B13 and Comparative Example B1. FIG. 29 is a graph showing the results of differential scanning calorimetry of Example B14 and Comparative Example B1. FIG. 30 is a graph showing the results of differential scanning calorimetry of Example B15 and Comparative Example B1. It is a graph showing the results of differential scanning calorimetry of Comparative Example B2 and Comparative Example B1. It is a graph showing the results of differential scanning calorimetry of Comparative Example B7 and Comparative Example B1. It is a graph showing the results of differential scanning calorimetry of Comparative Example B11 and Comparative Example B1. It is a graph showing the results of differential scanning calorimetry of Comparative Example B15 and Comparative Example B1. It is a graph showing the results of differential scanning calorimetry of Comparative Example B20 and Comparative Example B1. It is a graph showing the results of differential scanning calorimetry of Comparative Example B23 and Comparative Example B1. It is a graph showing the results of differential scanning calorimetry of Comparative Example B25 and Comparative Example B1. It is a graph showing the results of differential scanning calorimetry of Comparative Example B27 and Comparative Example B1. It is a graph showing the results of differential scanning calorimetry of Comparative Example B30 and Comparative Example B1. It is a graph showing the results of differential scanning calorimetry of Comparative Example B31 and Comparative Example B1. It is a graph showing the results of differential scanning calorimetry of Comparative Example B34 and Comparative Example B1. FIG. 42 is a graph showing the characteristics of the cold storage material during cooling. FIG. 43 is a graph showing the characteristics of the cold storage material during heating.

(Definition of terms)
The term "effective heat of fusion" as used herein means a heat of fusion within a range of 2 degrees Celsius or more and 8 degrees Celsius or less.
The term "ineffective heat of fusion" as used herein means the heat of fusion outside the range of 2 degrees Celsius or more and 8 degrees Celsius or less.
Heat of fusion can be measured using a differential scanning calorimeter (which may also be referred to as "DSC"), as is well known in the regenerator composition art. As demonstrated in the Examples described below, the differential scanning calorific value of the cold storage material composition is measured using a differential scanning calorimeter. The differential scanning calorimetry results are shown in the graph. See FIGS. 1-15 and 16-41. In the graph, the horizontal and vertical axes represent temperature and normalized heat flow, respectively. The heat of fusion in the range of 2 degrees Celsius or more and 8 degrees Celsius or less is equal to the integral value of the differential scanning calorific value in the range of 2 degrees Celsius or more and 8 degrees Celsius or less in the graph. Similarly, the heat of fusion in the range from 5 degrees Celsius to 12 degrees Celsius is equal to the integral value of the differential scanning calorific value in the range from 5 degrees Celsius to 12 degrees Celsius in the graph.
The term "refrigerator" as used herein refers to electric refrigerators and portable cooler boxes that are internally cooled. The term "cold storage" as used herein refers to a building whose interior is cooled.

Embodiments of the present invention will be described below.

FIG. 42 is a graph showing the characteristics of the cold storage material composition during cooling. In FIG. 42, the horizontal and vertical axes indicate time and temperature, respectively.

The cold storage material composition is cooled. See section A included in FIG. Unlike the case of a general liquid, as is well known in the technical field of cold storage material compositions, even if the temperature of the cold storage material composition reaches its melting point due to cooling of the cold storage material composition, The composition does not solidify and becomes supercooled. See section B included in FIG. In the supercooled state, the cold storage material composition is liquid.

Then, the regenerator composition begins to crystallize spontaneously. As it crystallizes, the cool storage material composition emits crystallization heat that is approximately equal to latent heat. As a result, the temperature of the cold storage material composition begins to rise. See section C included in FIG. In this specification, the temperature at which the cold storage material composition spontaneously begins to crystallize is referred to as the "crystallization temperature."

ΔT represents the difference between the melting point and crystallization temperature of the cold storage material composition. ΔT may also be referred to as "degree of supercooling." By crystallizing the cold storage material composition in a supercooled state, the cold storage material composition turns into class hydrate crystals (see, for example, Patent Document 1). Here, the term clathrate hydrate crystal refers to a crystal formed when water molecules form a cage-shaped crystal through hydrogen bonding, and a substance other than water is enclosed within the cage-shaped crystal. Unless otherwise specified, the term "clathrate hydrate crystal" herein includes not only clathrate hydrate crystals but also semiclathrate hydrate crystals. A semiclathrate hydrate crystal is a crystal formed when a guest molecule participates in a hydrogen bond network of water molecules. The concentration at which hydrate crystals are formed by the right amount of water molecules and guest molecules is called the harmonic concentration. Generally, hydrate crystals are often used near harmonic concentrations.

After the crystallization is completed and the heat of crystallization of the cool storage material composition is released, the temperature of the cool storage material composition gradually decreases to become equal to the ambient temperature. See section D included in FIG.

The crystallization temperature is lower than the melting point of the cold storage material composition. The melting point of a regenerator composition can be measured using a differential scanning calorimeter (which may also be referred to as "DSC"), as is well known in the regenerator composition art.

FIG. 43 is a graph showing the characteristics of the cold storage material composition during heating. In FIG. 43, the horizontal and vertical axes indicate time and temperature, respectively. During section E, the temperature of the cold storage material composition is maintained at a temperature below the crystallization temperature. For example, while the refrigerator door is closed, the temperature inside the refrigerator is set below the crystallization temperature so that the temperature of the cold storage material composition placed inside the refrigerator is maintained below the crystallization temperature. There is.

Next, the cold storage material composition is gradually heated. See section F included in FIG. For example, when the refrigerator door is opened (or when the door is opened and food is placed) at the end of section E (ie, at the beginning of section F), the temperature inside the refrigerator gradually increases.

When the temperature of the cold storage material composition reaches the melting point of the cold storage material composition, the temperature of the cold storage material composition is maintained near the melting point of the cold storage material composition. See section G included in FIG. In the unlikely event that there is no cold storage material composition, the temperature inside the refrigerator will rise continuously as shown in section Z included in FIG. 43. On the other hand, when the cold storage material composition is present, the temperature inside the refrigerator is maintained around the melting point of the cold storage material composition during the certain period of section G. In this way, the cold storage material composition exhibits a cold storage effect. At the end of section G, the crystals of the cold storage material composition melt and disappear. As a result, the cold storage material composition liquefies.

Thereafter, the temperature of the liquefied cold storage material composition rises to be equal to the ambient temperature. See section H included in FIG.

The regenerator composition can be cooled and reused. For example, after the door of the refrigerator is closed, as shown in section A included in FIG. 42, the cold storage material composition is cooled again and reused.

(First embodiment)
In the first embodiment, the following two conditions (AI) and (AII) must be satisfied for a cold storage material composition to be suitably used for a refrigerator.
Condition (AI) The cold storage material composition has a large heat of fusion of 135 joules/gram or more within a range of 2 degrees Celsius or more and 8 degrees Celsius or less.
Condition (AII) The cold storage material composition has a heat flow peak within a range of 2 degrees Celsius or more and 8 degrees Celsius or less.

The reason for condition (AI) and condition (AII) is that the internal temperature of the refrigerator should be maintained at a temperature of approximately 0 degrees Celsius or more and 12 degrees Celsius or less (for example, 2 degrees Celsius or more and 8 degrees Celsius or less). Because there is. In other words, if the temperature inside the cooler is maintained below 0 degrees Celsius, such a cooler is not a "refrigerator" but a "freezer". On the other hand, from the viewpoint of food preservation, if the temperature inside the cooler is maintained at a temperature higher than 12 degrees Celsius, such a cooler would have little practical use as a refrigerator.

The cold storage material according to the first embodiment is used not only for refrigerators but also for cold storages.

The cool storage material composition according to the first embodiment contains tetra-n-butylammonium bromide, water, and 1-propanol.

In the unlikely event that 1-butanol is not contained in the regenerator composition, the effective heat of fusion is equal to zero, as demonstrated in Comparative Example A1. Therefore, a cold storage material composition that does not contain 1-propanol is not suitable for refrigerators or cold storages.

If an alcohol other than 1-propanol is used, the effective heat of fusion is less than 135 Joules/gram, as demonstrated in Comparative Examples A2 to A13. In this case, since the section G (see FIG. 43) is shorter than that of the cold storage material composition according to the first embodiment, the cold storage efficiency of the cold storage material composition is lower than that of the cold storage material composition according to the first embodiment.

In the cold storage material composition according to the first embodiment, the weight ratio of tetra-n-butylammonium bromide to water is 37.5/62.5 (i.e., approximately 0.48) or more and 40/60 (i.e., approximately 0. .74) Below.

In the unlikely event that the weight ratio is less than 37.5/62.5 (i.e. approximately 0.48), the effective heat of fusion will be 135 Joules/ Less than a gram. Therefore, in this case, the cold storage efficiency of the cold storage material composition is low.

Should the weight ratio exceed 40/60 (ie, approximately 0.74), the effective heat of fusion will be less than 135 Joules/gram, as demonstrated in Comparative Examples A25-A26. Therefore, also in this case, the cold storage efficiency of the cold storage material composition is low.

In the cold storage material composition according to the first embodiment, the molar ratio of 1-propanol to water is 0.043 or more and 0.065 or less.

If the molar ratio is less than 0.043, the effective heat of fusion is less than 135 Joules/gram, as demonstrated in Comparative Examples A14 to A20. Therefore, in this case, the cold storage efficiency of the cold storage material composition is low.

If the molar ratio exceeds 0.065, the effective heat of fusion is less than 135 Joules/gram, as demonstrated in Comparative Example A21. Therefore, also in this case, the cold storage efficiency of the cold storage material composition is low.

As demonstrated in Examples A1 to A8, the cold storage material composition according to the first embodiment has a heat of fusion of 135 Joules/gram or more within a range of 2 degrees Celsius or more and 8 degrees Celsius or less. When the cold storage material composition according to the first embodiment is used, the section G (see FIG. 43) is long. Therefore, the cold storage material composition according to the first embodiment has high cold storage efficiency.

The cold storage material composition has a heat flow peak within a range of 2 degrees Celsius or more and 8 degrees Celsius or less. In the event that a cold storage material composition such as the cold storage material composition according to Comparative Example A1 is used that does not have a heat flow peak within the range of 2 degrees Celsius or more and 8 degrees Celsius or less, the invalid heat of fusion is effective. More than the heat of fusion. Therefore, in this case, the cold storage material composition is not suitable for a refrigerator or a cold storage because the cold storage efficiency is low within the range of 2 degrees Celsius or more and 8 degrees Celsius or less. In other words, the effective heat of fusion decreases as the heat flow peak becomes higher than 8 degrees Celsius or lower than 2 degrees Celsius. Therefore, if the cold storage material composition does not have a heat flow peak within the range of 2 degrees Celsius or more and 8 degrees Celsius or less, the cold storage efficiency within the range of 2 degrees Celsius or more and 8 degrees Celsius or less is low.

(Second embodiment)
In the second embodiment, the following two conditions (BI) and (BII) must be satisfied for a cold storage material composition to be suitably used for a refrigerator.
Condition (BI) The cold storage material composition has a large heat of fusion of 135 joules/gram or more within a range of 5 degrees Celsius or more and 12 degrees Celsius or less.
Condition (BII) The cold storage material composition has a heat flow peak within a range of 5 degrees Celsius or more and 12 degrees Celsius or less.

The reason for condition (BI) and condition (BII) is that the internal temperature of the refrigerator should be maintained at a temperature of approximately 0 degrees Celsius or more and 12 degrees Celsius or less (as an example, 5 degrees Celsius or more and 12 degrees Celsius or less). Because there is. In other words, if the temperature inside the cooler is maintained below 0 degrees Celsius, such a cooler is not a "refrigerator" but a "freezer". On the other hand, from the viewpoint of food preservation, if the temperature inside the cooler is maintained at a temperature higher than 12 degrees Celsius, such a cooler would have little practical use as a refrigerator.

The cold storage material according to the second embodiment is used not only for refrigerators but also for cold storages.

The cold storage material composition according to the second embodiment contains tetra-n-butylammonium bromide, water, and 1-propanol.

In the unlikely event that 1-butanol is not contained in the regenerator composition, the effective heat of fusion is equal to zero, as demonstrated in Comparative Example B1. Therefore, a cold storage material composition that does not contain 1-propanol is not suitable for refrigerators or cold storages.

If an alcohol other than 1-propanol is used, the effective heat of fusion is less than 135 Joules/gram, as demonstrated in Comparative Examples B2 to B13. In this case, since the section G (see FIG. 43) is shorter than that of the cold storage material composition according to the second embodiment, the cold storage efficiency of the cold storage material composition is lower than that of the cold storage material composition according to the second embodiment.

In the cold storage material composition according to the second embodiment, the weight ratio of tetra-n-butylammonium bromide to water is 32.5/67.5 (that is, approximately 0.48) or more and 42.5/57.5 ( That is, it is approximately 0.74) or less.

Should the weight ratio be less than 32.5/67.5 (i.e. approximately 0.48), the effective heat of fusion will be less than 135 Joules/gram, as demonstrated in Comparative Example B23. . Therefore, in this case, the cold storage efficiency of the cold storage material composition is low.

Should the weight ratio exceed 42.5/57.5 (ie, approximately 0.74), the effective heat of fusion will be less than 135 Joules/gram, as demonstrated in Comparative Example B24. Therefore, also in this case, the cold storage efficiency of the cold storage material composition is low.

In the cold storage material composition according to the second embodiment, the molar ratio of 1-propanol to water is 0.02 or more and 0.042 or less.

If the molar ratio is less than 0.02, the effective heat of fusion is less than 135 Joules/gram, as demonstrated in Comparative Example B14 and Comparative Example B15. Therefore, in this case, the cold storage efficiency of the cold storage material composition is low.

If the molar ratio exceeds 0.042, the effective heat of fusion is less than 135 Joules/gram, as demonstrated in Comparative Examples B16 to B22. Therefore, also in this case, the cold storage efficiency of the cold storage material composition is low.

As demonstrated in Examples B1 to B8, the cold storage material composition according to the second embodiment has a heat of fusion of 135 Joules/gram or more within the range of 5 degrees Celsius or more and 12 degrees Celsius or less. When the cold storage material composition according to the second embodiment is used, the section G (see FIG. 43) is long. Therefore, the cold storage material composition according to the second embodiment has high cold storage efficiency.

The cold storage material composition has a heat flow peak within a range of 5 degrees Celsius or more and 12 degrees Celsius or less. In the event that a cold storage material composition such as the cold storage material composition according to Comparative Example B1 that does not have a heat flow peak within the range of 5 degrees Celsius or more and 12 degrees Celsius or less is used, the invalid heat of fusion is effective. More than the heat of fusion. Therefore, in this case, the cold storage efficiency is low within the range of 5 degrees Celsius or more and 12 degrees Celsius or less, so the cold storage material composition is not suitable for refrigerators or cold storages. In other words, the effective heat of fusion decreases as the heat flow peak becomes higher than 12 degrees Celsius or lower than 5 degrees Celsius. Therefore, if the cold storage material composition does not have a heat flow peak within the range of 5 degrees Celsius or more and 12 degrees Celsius or less, the cold storage efficiency within the range of 5 degrees Celsius or more and 12 degrees Celsius or less is low.

(Third embodiment)
Similar to the second embodiment, in the third embodiment, the following two conditions (BI) and (BII) must be satisfied for a cold storage material composition to be suitably used for a refrigerator.
Condition (BI) The cold storage material composition has a large heat of fusion of 135 joules/gram or more within a range of 5 degrees Celsius or more and 12 degrees Celsius or less.
Condition (BII) The cold storage material composition has a heat flow peak within a range of 5 degrees Celsius or more and 12 degrees Celsius or less.

The reason for condition (BI) and condition (BII) is that the internal temperature of the refrigerator should be maintained at a temperature of approximately 0 degrees Celsius or more and 12 degrees Celsius or less (as an example, 5 degrees Celsius or more and 12 degrees Celsius or less). Because there is. In other words, if the temperature inside the cooler is maintained below 0 degrees Celsius, such a cooler is not a "refrigerator" but a "freezer". On the other hand, from the viewpoint of food preservation, if the temperature inside the cooler is maintained at a temperature higher than 12 degrees Celsius, such a cooler would have little practical use as a refrigerator.

The cold storage material according to the third embodiment is used not only for refrigerators but also for cold storages.

The cool storage material composition according to the third embodiment contains tetra-n-butylammonium bromide, water, and 1-butanol.

Problems when 1-butanol is not contained in the cool storage material composition and when alcohols other than 1-butanol are used are explained in the second embodiment.

In the cold storage material composition according to the third embodiment, the weight ratio of tetra-n-butylammonium bromide to water is 30/70 (that is, approximately 0.43) or more and 42.5/57.5 (that is, approximately 0). .74) Below.

Should the weight ratio be less than 30/70 (i.e. approximately 0.48), the effective heat of fusion will be less than 135 Joules/gram, as demonstrated in Comparative Example B31 and Comparative Example B32. . Therefore, in this case, the cold storage efficiency of the cold storage material composition is low.

In the unlikely event that the weight ratio exceeds 42.5/57.5 (i.e., approximately 0.74), the effective heat of fusion will be 135 Joules/gram, as demonstrated in Comparative Example B33 and Comparative Example B34. less than Therefore, also in this case, the cold storage efficiency of the cold storage material composition is low.

In the cold storage material composition according to the third embodiment, the molar ratio of 1-butanol to water is 0.02 or more and 0.035 or less.

If the molar ratio is less than 0.02, the effective heat of fusion is less than 135 Joules/gram, as demonstrated in Comparative Example B26 and Comparative Example B27. Therefore, in this case, the cold storage efficiency of the cold storage material composition is low.

If the molar ratio exceeds 0.035, the effective heat of fusion is less than 135 Joules/gram, as demonstrated in Comparative Example B28 and Comparative Example B29. Therefore, also in this case, the cold storage efficiency of the cold storage material composition is low.

Similar to the cold storage material composition according to the second embodiment, the cold storage material composition according to the third embodiment, as demonstrated in Examples B9 to B15, It has a heat of fusion of 135 joules/gram or more. When the cold storage material composition according to the third embodiment is used, the section G (see FIG. 43) is long. Therefore, the cold storage material composition according to the third embodiment has high cold storage efficiency.

Similar to the cold storage material composition according to the second embodiment, the cold storage material composition according to the third embodiment has a heat flow peak within a range of 5 degrees Celsius or more and 12 degrees Celsius or less.

(Example)
The invention will be explained in more detail with reference to the following examples.

(Example A1)
(Method for producing heat storage material composition)
First, tetra-n-butylammonium bromide (40 grams) and water (60 grams) were mixed inside a screw tube with a capacity of 110 milliliters to obtain a liquid mixture. The screw tube was a glass tube with a threaded cap.

Next, the mixed liquid (9.06 grams) was removed from a screw tube with a capacity of 110 ml, and then the mixed liquid (9.06 grams) was fed into a screw tube with a capacity of 60 ml. Additionally, 1-propanol (0.94 grams, manufactured by Fuji Film Wako Pure Chemical Industries, Ltd.) was added to a screw tube with a capacity of 60 milliliters. 1-propanol was used as an additive. In this way, a heat storage material composition according to Example A1 was obtained.

(Measurement experiment)
The heat storage material composition according to Example A1 (2 milligrams) was fed into a container (obtained from PerkinElmer, trade name: 02192005). The container was incorporated into a differential scanning calorimeter (obtained from PerkinElmer, trade name: DSC-8500). The cold storage material composition contained inside the container is cooled from room temperature to minus 30 degrees Celsius at a rate of 1 degree Celsius/minute, and then the cold storage material composition is left standing at minus 30 degrees Celsius for 5 minutes. , the cold storage material was crystallized.

The crystallized cold storage material composition was heated from -30 degrees Celsius to 30 degrees Celsius at a rate of 1 degree Celsius/minute. In this way, the crystallized cold storage material was melted.

While the crystallized regenerator composition is heated from -30 degrees Celsius to 30 degrees Celsius at a rate of 1 degree Celsius/minute as described above, the differential scanning calorimeter measures the heat flow (in watts). was output.
The normalized heat flow was calculated according to the following formula.
(normalized heat flow, unit: W/g) = (heat flow)/(weight of cold storage material, i.e. 2 milligrams)
FIG. 1 is a graph showing the results of differential scanning calorimetry performed in this manner.
The integral value of the differential scanning calorific value in the range from 2 degrees Celsius to 8 degrees Celsius in FIG. 1 was calculated as the effective heat of fusion within the range from 2 degrees Celsius to 8 degrees Celsius. See also FIG. 2 of Non-Patent Document 1.

As a result, the cold storage material composition according to Example A1 had an effective heat of fusion of 135.2 Joules/gram.

(Example A2)
In Example A2, the same experiment as Example A1 was performed, except that the molar ratio of additive to water was 0.045. FIG. 2 is a graph showing a comparison of DSC measurement results between Example A2 and Comparative Example A1.

(Example A3)
In Example A3, the same experiment as Example A1 was performed except that the molar ratio of additive to water was 0.047. FIG. 3 is a graph showing a comparison of DSC measurement results between Example A3 and Comparative Example A1.

(Example A4)
In Example A4, the same experiment as Example A1 was conducted, except that the molar ratio of additive to water was 0.052. FIG. 4 is a graph showing a comparison of DSC measurement results between Example A4 and Comparative Example A1.

(Example A5)
In Example A5, the same experiment as Example A1 was conducted, except that the molar ratio of additive to water was 0.06. FIG. 5 is a graph showing a comparison of DSC measurement results between Example A5 and Comparative Example A1.

(Example A6)
In Example A6, the same experiment as Example A1 was conducted, except that the molar ratio of additive to water was 0.065. FIG. 6 is a graph showing a comparison of DSC measurement results between Example A6 and Comparative Example A1.

(Example A7)
In Example A7, the same experiment as Example A2 was conducted, except that the weight ratio of tetra-n-butylammonium bromide to water was 37.5/62.5. FIG. 7 is a graph showing a comparison of DSC measurement results between Example A7 and Comparative Example A1.

(Comparative example A1)
In Comparative Example A1, the same experiment as Example A1 was conducted, except that no additives were added.

(Comparative example A2)
In Comparative Example A2, the same experiment as Example A4 was conducted, except that methanol (manufactured by Fuji Film Wako Pure Chemical Industries, Ltd.) was used as the additive.

(Comparative example A3)
In Comparative Example A3, the same experiment as Example A4 was conducted, except that ethanol (manufactured by Fuji Film Wako Pure Chemical Industries, Ltd.) was used as the additive. FIG. 8 is a graph showing a comparison of DSC measurement results between Comparative Example A3 and Comparative Example A1.

(Comparative example A4)
In Comparative Example A4, the same experiment as Example A4 was conducted, except that 2-propanol (manufactured by Fuji Film Wako Pure Chemical Industries, Ltd.) was used as the additive.

(Comparative example A5)
In Comparative Example A5, the same experiment as Example A4 was conducted, except that 1-butanol (manufactured by Fuji Film Wako Pure Chemical Industries, Ltd.) was used as the additive.

(Comparative example A6)
In Comparative Example A6, the same experiment as Example A4 was conducted, except that 2-butanol (manufactured by Fuji Film Wako Pure Chemical Industries, Ltd.) was used as the additive.

(Comparative example A7)
In Comparative Example A7, the same experiment as Example A4 was conducted, except that tert-butyl alcohol (manufactured by Tokyo Kasei Kogyo) was used as the additive. FIG. 9 is a graph showing a comparison of DSC measurement results between Comparative Example A7 and Comparative Example A1.

(Comparative example A8)
In Comparative Example A8, the same experiment as Example A4 was conducted, except that 1-pentanol (manufactured by Fuji Film Wako Pure Chemical Industries, Ltd.) was used as the additive.

(Comparative example A9)
In Comparative Example A9, the same experiment as Example A4 was conducted, except that 1-hexanol (manufactured by Fuji Film Wako Pure Chemical Industries, Ltd.) was used as the additive. FIG. 10 is a graph showing a comparison of DSC measurement results between Comparative Example A9 and Comparative Example A1.

(Comparative example A10)
In Comparative Example A10, the same experiment as Example A4 was conducted, except that ethylene glycol (manufactured by Fuji Film Wako Pure Chemical Industries, Ltd.) was used as the additive. FIG. 11 is a graph showing a comparison of DSC measurement results between Comparative Example A10 and Comparative Example A1.

(Comparative example A11)
In Comparative Example A11, the same experiment as Example A4 was conducted, except that glycerin (manufactured by Fuji Film Wako Pure Chemical Industries, Ltd.) was used as the additive.

(Comparative example A12)
In Comparative Example A12, the same experiment as Example A4 was conducted, except that meso-erythritol (manufactured by Tokyo Kasei Kogyo) was used as the additive.

(Comparative example A13)
In Comparative Example A13, the same experiment as Example A4 was conducted except that xylitol (manufactured by Fuji Film Wako Pure Chemical Industries, Ltd.) was used as the additive.

(Comparative example A14)
In Comparative Example A14, the same experiment as Example A1 was conducted, except that the molar ratio of additive to water was 0.011.

(Comparative example A15)
In Comparative Example A15, the same experiment as Example A1 was conducted, except that the molar ratio of additive to water was 0.015.

(Comparative example A16)
In Comparative Example A16, the same experiment as Example A1 was conducted, except that the molar ratio of additive to water was 0.02.

(Comparative example A17)
In Comparative Example A17, the same experiment as Example A1 was conducted, except that the molar ratio of additive to water was 0.022.

(Comparative example A18)
In Comparative Example A18, the same experiment as Example A1 was conducted, except that the molar ratio of additive to water was 0.035. FIG. 12 is a graph showing a comparison of DSC measurement results between Comparative Example A18 and Comparative Example A1.

(Comparative example A19)
In Comparative Example A19, the same experiment as Example A1 was conducted, except that the molar ratio of additive to water was 0.04.

(Comparative example A20)
In Comparative Example A20, the same experiment as Example A1 was conducted, except that the molar ratio of additive to water was 0.042.

(Comparative example A21)
In Comparative Example A21, the same experiment as Example A1 was conducted, except that the molar ratio of additive to water was 0.067. FIG. 13 is a graph showing a comparison of DSC measurement results between Comparative Example A21 and Comparative Example A1.

(Comparative example A22)
In Comparative Example A22, the same experiment as Example A4 was conducted, except that the weight ratio of tetra-n-butylammonium bromide to water was 30/70. FIG. 14 is a graph showing a comparison of DSC measurement results between Comparative Example A22 and Comparative Example A1.

(Comparative example A23)
In Comparative Example A23, the same experiment as Example A4 was conducted, except that the weight ratio of tetra-n-butylammonium bromide to water was 32.5/67.5.

(Comparative example A24)
In Comparative Example A24, the same experiment as Example A4 was conducted, except that the weight ratio of tetra-n-butylammonium bromide to water was 35/65.

(Comparative example A25)
In Comparative Example A25, the same experiment as Example A4 was conducted, except that the weight ratio of tetra-n-butylammonium bromide to water was 42.5/57.5.

(Comparative example A26)
In Comparative Example A26, the same experiment as Example A4 was conducted, except that the weight ratio of tetra-n-butylammonium bromide to water was 45/55. FIG. 15 is a graph showing a comparison of DSC measurement results between Comparative Example A26 and Comparative Example A1.

Tables 1 and 2 below show the results of Examples A1 to A7 and Comparative Examples A1 to A26.

As is clear from comparing Examples A1 to A7 with Comparative Example A1, if 1-propanol is not contained in the regenerator composition, the effective heat of fusion will decrease as demonstrated in Comparative Example A1. is equal to 0.

As is clear from comparing Examples A1 to A7 with Comparative Examples A2 to A13, if an alcohol other than 1-propanol is used, the effective heat of fusion will be 123.0 Joules/gram or less. This is a low value.

As is clear from comparing Examples A1 to A7 with Comparative Examples A22 to A24, if the weight ratio of tetra-n-butylammonium bromide to water is 35/65 (i.e., approximately 0.54 ), the effective heat of fusion will be as low as 115.9 Joules/gram or less.

As is clear from comparing Examples A1 to A7 with Comparative Examples A25 to A26, if the weight ratio of tetra-n-butylammonium bromide to water is 42.5/57.5 (i.e., (approximately 0.74), the effective heat of fusion is as low as 128.2 Joules/gram or less.

As is clear from comparing Examples A1 to A7 with Comparative Examples A14 to A20, if the molar ratio of the additive to water is 0.042 or less, the effective heat of fusion will be 126. The value is as low as 2 joules/gram or less.

As is clear from comparing Examples A1 to A7 with Comparative Example A21, if the molar ratio of the additive to water was 0.067, the effective heat of fusion would be 111.7 Joules/gram. becomes a low value.

As demonstrated in Example A1 to Example A7, when the additive is 1-propanol, the temperature will exceed 2 degrees Celsius and 8 degrees Celsius if the following two conditions (AI) and (AII) are met: A cold storage material composition having a heat of fusion of 135 joules/g or more can be obtained within the following range.
Condition (AI) The weight ratio of tetra-n-butylammonium bromide to water is 37.5/62.5 or more and 40/60 or less.
Condition (AII) The molar ratio of 1-propanol to water is 0.043 or more and 0.065 or less.

As is clear from FIGS. 1 to 15, each of the cold storage material compositions according to Examples A1 to A7 has a heat flow peak within a range of 2 degrees Celsius or more and 8 degrees Celsius or less. On the other hand, the cool storage material composition according to Comparative Example A1 has a heat flow peak at approximately 14.5 degrees Celsius.

(Example B1)
(Method for producing heat storage material composition)
First, tetra-n-butylammonium bromide (40 grams) and water (60 grams) were mixed inside a screw tube with a capacity of 110 milliliters to obtain a liquid mixture. The screw tube was a glass tube with a threaded cap.

Next, the mixed liquid (9.58 grams) was removed from a screw tube with a capacity of 110 ml, and then the mixed liquid (9.58 grams) was fed into a screw tube with a capacity of 60 ml. Additionally, 1-propanol (0.42 grams, manufactured by Fuji Film Wako Pure Chemical Industries, Ltd.) was added to a screw tube with a capacity of 60 milliliters. 1-propanol was used as an additive. In this way, a heat storage material composition according to Example B1 was obtained.

(Measurement experiment)
The heat storage material composition according to Example B1 (2 milligrams) was fed into a container (obtained from PerkinElmer, trade name: 02192005). The container was incorporated into a differential scanning calorimeter (obtained from PerkinElmer, trade name: DSC-8500). The cold storage material composition contained inside the container is cooled from room temperature to minus 30 degrees Celsius at a rate of 1 degree Celsius/minute, and then the cold storage material composition is left standing at minus 30 degrees Celsius for 5 minutes. , the cold storage material was crystallized.

The crystallized cold storage material composition was heated from -30 degrees Celsius to 30 degrees Celsius at a rate of 1 degree Celsius/minute. In this way, the crystallized cold storage material was melted.

While the crystallized regenerator composition is heated from -30 degrees Celsius to 30 degrees Celsius at a rate of 1 degree Celsius/minute as described above, the differential scanning calorimeter measures the heat flow (in watts). was output.
The normalized heat flow was calculated according to the following formula.
(normalized heat flow, unit: W/g) = (heat flow)/(weight of cold storage material, i.e. 2 milligrams)
FIG. 16 is a graph showing the results of differential scanning calorimetry performed in this manner.
The integral value of the differential scanning calorific value in the range from 5 degrees Celsius to 12 degrees Celsius in FIG. 16 was calculated as the effective heat of fusion within the range from 5 degrees Celsius to 12 degrees Celsius. See also FIG. 2 of Non-Patent Document 1.

As a result, the cold storage material composition according to Example B1 had an effective heat of fusion of 145.0 Joules/gram.

(Example B2)
In Example B2, the same experiment as Example B1 was performed, except that the molar ratio of additive to water was 0.022. FIG. 17 is a graph showing the DSC measurement results of Example B2 and Comparative Example B1.

(Example B3)
In Example B3, the same experiment as Example B1 was performed, except that the molar ratio of additive to water was 0.035. FIG. 18 is a graph showing the DSC measurement results of Example B3 and Comparative Example B1.

(Example B4)
In Example B4, the same experiment as Example B1 was performed, except that the molar ratio of additive to water was 0.04. FIG. 19 is a graph showing the DSC measurement results of Example B4 and Comparative Example B1.

(Example B5)
In Example B5, the same experiment as Example B1 was performed except that the molar ratio of additive to water was 0.042. FIG. 20 is a graph showing the DSC measurement results of Example B5 and Comparative Example B1.

(Example B6)
In Example B6, the same experiment as Example B2 was conducted, except that the weight ratio of tetra-n-butylammonium bromide to water was 32.5/67.5. FIG. 21 is a graph showing the DSC measurement results of Example B6 and Comparative Example B1.

(Example B7)
In Example B7, the same experiment as Example B2 was conducted, except that the weight ratio of tetra-n-butylammonium bromide to water was 35/65. FIG. 22 is a graph showing the DSC measurement results of Example B7 and Comparative Example B1.

(Example B8)
In Example B8, the same experiment as Example B2 was conducted, except that the weight ratio of tetra-n-butylammonium bromide to water was 42.5/57.5. FIG. 23 is a graph showing the DSC measurement results of Example B8 and Comparative Example B1.

(Example B9)
In Example B9, the same experiment as Example B1 was conducted, except that 1-butanol (manufactured by Fuji Film Wako Pure Chemical Industries, Ltd.) was used as the additive. FIG. 24 is a graph showing the DSC measurement results of Example B9 and Comparative Example B1.

(Example B10)
In Example B10, the same experiment as Example B9 was conducted, except that the molar ratio of additive to water was 0.022. FIG. 25 is a graph showing the DSC measurement results of Example B10 and Comparative Example B1.

(Example B11)
In Example B11, the same experiment as Example B9 was conducted, except that the molar ratio of additive to water was 0.033. FIG. 26 is a graph showing the DSC measurement results of Example B11 and Comparative Example B1.

(Example B12)
In Example B12, the same experiment as Example B9 was conducted, except that the molar ratio of additive to water was 0.035. FIG. 27 is a graph showing the DSC measurement results of Example B12 and Comparative Example B1.

(Example B13)
In Example B13, the same experiment as Example B10 was conducted, except that the weight ratio of tetra-n-butylammonium bromide to water was 30/70. FIG. 28 is a graph showing the DSC measurement results of Example B13 and Comparative Example B1.

(Example B14)
In Example B14, the same experiment as Example B10 was conducted, except that the weight ratio of tetra-n-butylammonium bromide to water was 35/65. FIG. 29 is a graph showing the DSC measurement results of Example B14 and Comparative Example B1.

(Example B15)
In Example B15, the same experiment as Example B10 was conducted, except that the weight ratio of tetra-n-butylammonium bromide to water was 42.5/57.5. FIG. 30 is a graph showing the DSC measurement results of Example B15 and Comparative Example B1.

(Comparative example B1)
In Comparative Example B1, the same experiment as Example B1 was conducted, except that no additives were added.

(Comparative example B2)
In Comparative Example B2, the same experiment as in Example B2 was conducted, except that methanol (manufactured by Fuji Film Wako Pure Chemical Industries, Ltd.) was used as the additive. FIG. 31 is a graph showing the DSC measurement results of Comparative Example B2 and Comparative Example B1.

(Comparative example B3)
In Comparative Example B3, the same experiment as in Example B2 was conducted, except that ethanol (manufactured by Fuji Film Wako Pure Chemical Industries, Ltd.) was used as the additive.

(Comparative example B4)
In Comparative Example B4, the same experiment as Example B2 was conducted, except that 2-propanol (manufactured by Fuji Film Wako Pure Chemical Industries, Ltd.) was used as the additive.

(Comparative example B5)
In Comparative Example B5, the same experiment as Example B2 was conducted, except that 2-butanol (manufactured by Fuji Film Wako Pure Chemical Industries, Ltd.) was used as the additive.

(Comparative example B6)
In Comparative Example B6, the same experiment as Example B2 was conducted, except that tert-butyl alcohol (manufactured by Tokyo Kasei Kogyo) was used as the additive.

(Comparative example B7)
In Comparative Example B7, the same experiment as in Example B2 was conducted, except that 1-pentanol (manufactured by Fuji Film Wako Pure Chemical Industries, Ltd.) was used as the additive. FIG. 32 is a graph showing the DSC measurement results of Comparative Example B7 and Comparative Example B1.

(Comparative example B8)
In Comparative Example B8, the same experiment as in Example B2 was conducted, except that 1-hexanol (manufactured by Fuji Film Wako Pure Chemical Industries, Ltd.) was used as the additive.

(Comparative example B9)
In Comparative Example B9, the same experiment as in Example B2 was conducted, except that ethylene glycol (manufactured by Fuji Film Wako Pure Chemical Industries, Ltd.) was used as the additive.

(Comparative example B10)
In Comparative Example B10, the same experiment as Example B2 was conducted, except that 1,4-butanediol (manufactured by Fuji Film Wako Pure Chemical Industries, Ltd.) was used as the additive.

(Comparative example B11)
In Comparative Example B11, the same experiment as in Example B2 was conducted, except that glycerin (manufactured by Fuji Film Wako Pure Chemical Industries, Ltd.) was used as the additive. FIG. 33 is a graph showing the DSC measurement results of Comparative Example B11 and Comparative Example B1.

(Comparative example B12)
In Comparative Example B12, the same experiment as Example B2 was conducted, except that meso-erythritol (manufactured by Tokyo Kasei Kogyo) was used as the additive.

(Comparative example B13)
In Comparative Example B13, the same experiment as Example B2 was conducted, except that xylitol (manufactured by Fuji Film Wako Pure Chemical Industries, Ltd.) was used as the additive.

(Comparative example B14)
In Comparative Example B14, the same experiment as Example B1 was conducted, except that the molar ratio of additive to water was 0.011.

(Comparative example B15)
In Comparative Example B15, the same experiment as Example B1 was conducted, except that the molar ratio of additive to water was 0.015. FIG. 34 is a graph showing the DSC measurement results of Comparative Example B15 and Comparative Example B1.

(Comparative example B16)
In Comparative Example B16, the same experiment as Example B1 was conducted, except that the molar ratio of additive to water was 0.043.

(Comparative example B17)
In Comparative Example B17, the same experiment as Example B1 was conducted, except that the molar ratio of additive to water was 0.045.

(Comparative example B18)
In Comparative Example B18, the same experiment as Example B1 was conducted, except that the molar ratio of additive to water was 0.047.

(Comparative example B19)
In Comparative Example B19, the same experiment as Example B1 was conducted, except that the molar ratio of additive to water was 0.052.

(Comparative example B20)
In Comparative Example B20, the same experiment as Example B1 was conducted, except that the molar ratio of additive to water was 0.06. FIG. 35 is a graph showing the DSC measurement results of Comparative Example B20 and Comparative Example B1.

(Comparative example B21)
In Comparative Example B21, the same experiment as Example B1 was conducted, except that the molar ratio of additive to water was 0.065.

(Comparative example B22)
In Comparative Example B22, the same experiment as Example B1 was conducted, except that the molar ratio of additive to water was 0.067.

(Comparative example B23)
In Comparative Example B23, the same experiment as Example B2 was conducted, except that the weight ratio of tetra-n-butylammonium bromide to water was 30/70. FIG. 36 is a graph showing the DSC measurement results of Comparative Example B23 and Comparative Example B1.

(Comparative example B24)
In Comparative Example B24, the same experiment as Example B2 was conducted, except that the weight ratio of tetra-n-butylammonium bromide to water was 45/55.

(Comparative example B25)
In Comparative Example B25, the same experiment as Example B2 was conducted, except that the weight ratio of tetra-n-butylammonium bromide to water was 50/50. FIG. 37 is a graph showing the DSC measurement results of Comparative Example B25 and Comparative Example B1.

(Comparative example B26)
In Comparative Example B26, the same experiment as Example B9 was conducted, except that the molar ratio of additive to water was 0.011.

(Comparative example B27)
In Comparative Example B27, the same experiment as Example B9 was conducted, except that the molar ratio of additive to water was 0.015. FIG. 38 is a graph showing the DSC measurement results of Comparative Example B27 and Comparative Example B1.

(Comparative example B28)
In Comparative Example B28, the same experiment as Example B9 was conducted, except that the molar ratio of additive to water was 0.04.

(Comparative example B29)
In Comparative Example B29, the same experiment as Example B9 was conducted, except that the molar ratio of additive to water was 0.043.

(Comparative example B30)
In Comparative Example B30, the same experiment as Example B9 was conducted, except that the molar ratio of additive to water was 0.052. FIG. 39 is a graph showing the DSC measurement results of Comparative Example B30 and Comparative Example B1.

(Comparative example B31)
In Comparative Example B31, the same experiment as Example B10 was conducted, except that the weight ratio of tetra-n-butylammonium bromide to water was 22.5/77.5. FIG. 40 is a graph showing the DSC measurement results of Comparative Example B31 and Comparative Example B1.

(Comparative example B32)
In Comparative Example B32, the same experiment as Example B10 was conducted, except that the weight ratio of tetra-n-butylammonium bromide to water was 25/75.

(Comparative example B33)
In Comparative Example B33, the same experiment as Example B10 was conducted, except that the weight ratio of tetra-n-butylammonium bromide to water was 45/55.

(Comparative example B34)
In Comparative Example B34, the same experiment as Example B10 was conducted, except that the weight ratio of tetra-n-butylammonium bromide to water was 50/50. FIG. 41 is a graph showing the DSC measurement results of Comparative Example B34 and Comparative Example B1.

Tables 3 and 4 below show the results of Examples B1 to B15 and Comparative Examples B1 to B34.

As is clear from comparing Examples B1 to B15 with Comparative Example B1, if at least one selected from the group consisting of 1-propanol and 1-butanol is not contained in the cold storage material composition, As demonstrated in Comparative Example B1, the effective heat of fusion is equal to zero.

As is clear from comparing Examples B1 to B15 with Comparative Examples B2 to B13, if an alcohol other than at least one selected from the group consisting of 1-propanol and 1-butanol is used. In this case, the effective heat of fusion is as low as 134.7 joules/gram or less.

When the additive is 1-propanol, as is clear from comparing Examples B1 to B8 with Comparative Example B23, if the weight ratio of tetra-n-butylammonium bromide to water is 30/70 ( (approximately 0.43), the effective heat of fusion is as low as 130.1 Joules/gram.

When the additive is 1-propanol, as is clear from comparing Examples B1 to B8 with Comparative Example B24, if the weight ratio of tetra-n-butylammonium bromide to water is 45/55 ( (approximately 0.82), the effective heat of fusion is as low as 124.4 Joules/gram.

When the additive is 1-propanol, as is clear from comparing Examples B1 to B8 with Comparative Example B14 and Comparative Example B15, if the molar ratio of the additive to water is 0.015 or less. In this case, the effective heat of fusion is as low as 126.9 Joules/gram or less.

When the additive is 1-propanol, as is clear from comparing Examples B1 to B8 with Comparative Examples B16 to B22, if the molar ratio of the additive to water is 0.043 or more. In this case, the effective heat of fusion is as low as 133.7 Joules/gram or less.

As demonstrated in Examples B1 to B8, when the additive is 1-propanol, if the following two conditions (Bi) and (ii) are met, the temperature will exceed 5 degrees Celsius and 12 degrees Celsius. A cold storage material composition having a heat of fusion of 135 joules/g or more can be obtained within the following range.
Condition (Bi) The weight ratio of tetra-n-butylammonium bromide to water is 32.5/67.5 or more and 42.5/57.5 or less.
Condition (Bii) The molar ratio of 1-propanol to water is 0.02 or more and 0.042 or less.

When the additive is 1-butanol, as is clear from comparing Examples B9 to B15 with Comparative Example B31 and Comparative Example B32, if the weight ratio of tetra-n-butylammonium bromide to water is 25/75 (or approximately 0.33), the effective heat of fusion will be as low as 116.0 Joules/gram or less.

When the additive is 1-butanol, as is clear from comparing Examples B9 to B15 with Comparative Example B33 and Comparative Example B34, if the weight ratio of tetra-n-butylammonium bromide to water is 45/55 (ie, approximately 0.82), the effective heat of fusion will be as low as 117.5 Joules/gram or less.

When the additive is 1-butanol, as is clear from comparing Examples B9 to B15 with Comparative Example B26 and Comparative Example B27, if the molar ratio of the additive to water is 0.015 or less. In this case, the effective heat of fusion is as low as 109.3 Joules/gram or less.

When the additive is 1-butanol, as is clear from comparing Examples B9 to B15 to Comparative Examples B28 to B30, if the molar ratio of the additive to water is 0.040 or more. In this case, the effective heat of fusion is as low as 132.8 Joules/gram or less.

As demonstrated in Example B9 to Example B15, when the additive is 1-butanol, the temperature will exceed 5 degrees Celsius and 12 degrees Celsius if the following two conditions (Biii) and (iv) are met: A cold storage material composition having a heat of fusion of 135 joules/g or more can be obtained within the following range.
Condition (Biii) The weight ratio of tetra-n-butylammonium bromide to water is 30/70 or more and 42.5/57.5 or less.
Condition (Biv) The molar ratio of 1-butanol to water is 0.02 or more and 0.035 or less.

As is clear from FIGS. 16 to 41, each of the cold storage material compositions according to Examples B1 to B15 has a heat flow peak within a range of 5 degrees Celsius or more and 12 degrees Celsius or less. On the other hand, the cool storage material composition according to Comparative Example B1 has a heat flow peak at approximately 14.5 degrees Celsius.

The cold storage material composition according to the first aspect of the present invention may be included in a refrigerator or a cold storage box whose internal temperature is maintained at a temperature of 2 degrees Celsius or more and 8 degrees Celsius or less.
The cold storage material composition according to the second aspect of the present invention may be included in a refrigerator or a cold storage box whose internal temperature is maintained at a temperature of 5 degrees Celsius or more and 12 degrees Celsius or less. The cold storage material composition according to the third aspect of the present invention may also be included in a refrigerator or cold storage whose internal temperature is maintained at a temperature of 5 degrees Celsius or more and 12 degrees Celsius or less.

Claims (9)

A cold storage material composition,
Tetra-n-butylammonium bromide,
Contains water and 1-propanol,
The weight ratio of the tetra-n-butylammonium bromide to the water is 37.5/62.5 or more and 40/60 or less,
The molar ratio of the 1-propanol to the water is 0.043 or more and 0.065 or less,
The cold storage material composition has a heat of fusion of 135 joules/gram or more within a range of 2 degrees Celsius or more and 8 degrees Celsius or less, and the cold storage material composition has a heat flow within a range of 2 degrees Celsius or more and 8 degrees Celsius or less. having a peak,
Cold storage material composition. A refrigerator comprising the cold storage material composition according to claim 1. A cold storage comprising the cold storage material composition according to claim 1. A cold storage material composition,
Tetra-n-butylammonium bromide,
Contains water and 1-propanol,
The weight ratio of the tetra-n-butylammonium bromide to the water is 32.5/67.5 or more and 42.5/57.5 or less,
The molar ratio of the 1-propanol to the water is 0.02 or more and 0.042 or less,
The cold storage material composition has a heat of fusion of 135 joules/gram or more within a range of 5 degrees Celsius or more and 12 degrees Celsius or less, and the cold storage material composition has a heat flow within a range of 5 degrees Celsius or more and 12 degrees Celsius or less. having a peak,
Cold storage material composition. A refrigerator comprising the cold storage material composition according to claim 4. A cold storage box comprising the cold storage material composition according to claim 4. A cold storage material composition,
Tetra-n-butylammonium bromide,
Contains water and 1-butanol,
The weight ratio of the tetra-n-butylammonium bromide to the water is 30/70 or more and 42.5/57.5 or less,
The molar ratio of the 1-butanol to the water is 0.02 or more and 0.035 or less,
The cold storage material composition has a heat of fusion of 135 joules/gram or more within a range of 5 degrees Celsius or more and 12 degrees Celsius or less, and the cold storage material composition has a heat flow within a range of 5 degrees Celsius or more and 12 degrees Celsius or less. having a peak,
Cold storage material composition. A refrigerator comprising the cold storage material composition according to claim 7. A cold storage box comprising the cold storage material composition according to claim 7.

Images